Conspectus
Galvanic replacement synthesis
involves oxidation and dissolution
of atoms from a substrate while the salt precursor to another material
with a higher reduction potential is reduced and deposited on the
substrate. The driving force or spontaneity of such a synthesis comes
from the difference in reduction potential between the redox pairs
involved. Both bulk and micro/nanostructured materials have been explored
as substrates for galvanic replacement synthesis. The use of micro/nanostructured
materials can significantly increase the surface area, offering immediate
advantages over the conventional electrosynthesis. The micro/nanostructured
materials can also be intimately mixed with the salt precursor in
a solution phase, resembling the setting of a typical chemical synthesis.
The reduced material tends to be directly deposited on the surface
of the substrate, just like the situation in an electrosynthesis.
Different from an electrosynthesis where the two electrodes are spatially
separated by an electrolyte solution, the cathodes and anodes are
situated on the same surface, albeit at different sites, even for
a micro/nanostructured substrate. Since the oxidation and dissolution
reactions occur at sites different from those for reduction and deposition
reactions, one can control the growth pattern of the newly deposited
atoms on the same surface of a substrate to access nanostructured
materials with diverse and controllable compositions, shapes, and
morphologies in a single step. Galvanic replacement synthesis has
been successfully applied to different types of substrates, including
those made of crystalline and amorphous materials, as well as metallic
and nonmetallic materials. Depending on the substrate involved, the
deposited material can take different nucleation and growth patterns,
resulting in diverse but well-controlled nanomaterials sought for
a variety of studies and applications.
In this Account, we recapitulate
our efforts over the past two
decades in fabricating metal nanostructures for a broad range of applications
by leveraging the unique capability of galvanic replacement synthesis.
We begin with a brief introduction to the fundamentals of galvanic
replacement between metal nanocrystals and salt precursors, followed
by a discussion of the roles played by surface capping agents in achieving
site-selected carving and deposition for the fabrication of various
bimetallic nanostructures. Two examples based on the Ag–Au
and Pd–Pt systems are selected to illustrate the concept and
mechanism. We then highlight our recent work on the galvanic replacement
synthesis involving nonmetallic substrates, with a focus on the protocol,
mechanistic understanding, and experimental control for the fabrication
of Au- and Pt-based nanostructures with tunable morphologies. Finally,
we showcase the unique properties and applications of nanostructured
materials derived from galvanic replacement reactions for biomedicine
and catalysis. We also offer some perspectives on the challenges and
opportunities in this emerg...